CN102906146B - Use the hot melt adhesion of thermoplastic polyurethane - Google Patents

Use the hot melt adhesion of thermoplastic polyurethane Download PDF

Info

Publication number
CN102906146B
CN102906146B CN201180026152.3A CN201180026152A CN102906146B CN 102906146 B CN102906146 B CN 102906146B CN 201180026152 A CN201180026152 A CN 201180026152A CN 102906146 B CN102906146 B CN 102906146B
Authority
CN
China
Prior art keywords
tpu
mol
compound
diisocyanate
index
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201180026152.3A
Other languages
Chinese (zh)
Other versions
CN102906146A (en
Inventor
M·布杜
O·S·亨策
D·肯普弗特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of CN102906146A publication Critical patent/CN102906146A/en
Application granted granted Critical
Publication of CN102906146B publication Critical patent/CN102906146B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2250/00—Compositions for preparing crystalline polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to a kind of improved method of the hot melt adhesion based on thermoplastic polyurethane,Wherein using adhesive can be used as by the obtained thermoplastic polyurethane (TPU) of symmetrical aliphatic diisocyanate A and at least one isocyanate-reactive compound B comprising hydroxyl and/or amino substantially,Wherein compound B number-average molecular weight (Mn) is at least 2200g/mol,Condition is if compound B is sebacate,Then it is at least 950g/mol,Diisocyanate A and at least one isocyanate-reactive compound B react in the presence of the catalyst for sudden reaction,TPU does not include cahin extension agent,TPU, which has, is less than 1000,Preferably smaller than 990,More preferably less than 980 index IN,And carried out in the absence of solvent at a temperature of 50 160 DEG C by the melting adhered of molten state TPU,And the base material by its bonding.

Description

Use the hot melt adhesion of thermoplastic polyurethane
Base material the present invention relates to the melting adhered improved method based on thermoplastic polyurethane (TPU) and by its bonding.
It is known using thermoplastic polyurethane as hot-melt adhesive.Hot-melt adhesive can realize solvent-free 100% The interconnection technique of solid binder system, it uses and does not both need solvent recovery unit, it is not required that is using water-based adhesive Evaporation water during system.Hot-melt adhesive application in the form of hot melt, rapid curing during cooling, thus establishes its intensity.
Produced by the known reactions using diisocyanate and the esterification products formed by alkane dicarboxylic acid of DE-B 1256822 The melt or solution of thing are as adhesive to bond polyvinyl chloride polymer.DE-A1930336 and DE 3717070A1 are disclosed Contain terminal hydroxyl and can be used as by the polyester-polyurethane that polyester-diol, cahin extension agent and organic diisocyanate react to obtain The purposes of solvent-based adhesive.DE 4035280A1 disclose the crystallization hot melt comprising isocyanate groups and based on prepolymer Adhesive.Such as other reactive hot-melt adhesives with terminal isocyanate, such as DE 10163857A1, DE It is that they react with moisture the shortcomings that type described in 19700014A1 and DE 19519391A1, therefore produces bubble, this is to many It is unacceptable for purpose, and with the very long reaction time, and high temperature is needed in preparation process.
In this area TPU bases hot-melt adhesive used be usually block and containing so-called hard and soft chain segment.Hard chain Section is reacted to obtain by diisocyanate with low-molecular-weight chain extender, and soft chain segment is excellent by diisocyanate and such as molecular weight Polyalcohol of the choosing more than 499g/mol or polyamines react and obtained.The shortcomings that this kind of hot-melt adhesive is that they are more than 160 DEG C Processing temperature and their corresponding high melt viscosities.
It is known per se to prepare block TPU-referring to Iskender and Yilgor, Polymer Reviews without cahin extension agent, 47:487-510,2007.According to US 2005/0288476A1, inlay section thermal plastic polyurethane can pass through hydroxyl or amine block polymerization Thing or oligomer obtain as soft chain segment with diisocyanate in the absence of stoichiometric reaction under cahin extension agent.These TPU contain It is said that there is so-called single dispersing hard segment and can be processed with melt.However, do not propose them as hot-melt adhesive Purposes.
TPU bases hot-melt adhesive used typically has high-melting-point in this area that can be prepared in extruder (i.e. higher than 160 DEG C), this makes processing difficult.
It is an object of the invention to provide the melting adhered improvement side that can be carried out under low melting glass and low melt viscosity Method, wherein using easily and it is quick prepare and hot-melt adhesive that is quick and being bonded with low number of bubbles, therefore to save Energy simultaneously realizes user to high production rate and an urgent demand to mechanical strength simultaneously.
The present invention, which provides use, to include hydroxyl and/or amino by symmetrical aliphatic diisocyanate A and at least one substantially Melting adhered method of the obtained thermoplastic polyurethanes (TPU) of isocyanate-reactive compound B as adhesive, wherein：
- compound B number-average molecular weight (Mn) is at least 2200g/mol, condition be if compound B is sebacate, Then it is at least 950g/mol,
- diisocyanate A and isocyanate-reactive compound B react in the presence of the catalyst for sudden reaction,
- TPU does not include cahin extension agent,
- TPU has the index IN less than 1000,
- carried out in the absence of solvent at a temperature of 50-160 DEG C by the melting adhered of molten state TPU.
This method is carried out in the absence of solvent, and wherein solvent means to dissolve TPU material, more particularly dimethyl formyl Amine, MEK, ethyl acetate, acetone, dichloromethane or tetrahydrofuran.
TPU used according to the invention does not include cahin extension agent, and wherein cahin extension agent means have at least two isocyanates anti- The compound of answering property group, more particularly hydroxyl or amino, and this kind of compound has 499g/mol or smaller molecular weight.It is special It is not that typical cahin extension agent, such as such as Isosorbide-5-Nitrae-fourth two of the linear alkanediol with two or more carbon atoms are not present in TPU Alcohol and 1,6-HD.
It is particularly apparent the method have the advantages that using can be in an extruder in a work in the case of preferred embodiment The cheap thermoplastic polyurethane prepared in skill step.The advantages of material be it due to shorter crystallization time, preferably small In rapid curing in 1 hour, therefore also allow for being thermally bonded faster.In addition, during preparation and particularly in the heat bonding phase Between, it is necessary to relatively low temperature, and these temperature allow more easily to handle, and provide to wide variety of sizable section Energy.
In an especially preferred embodiment, thermoplastic polyurethane has 850-999, preferably 850-990, more preferably 850-980 index.
Index is by component A used total isocyanate groups in reaction and component B isocyanate-reactive group, i.e., The mol ratio definition of reactive hydrogen.With 1000 index, for component A each isocyanate groups, component (B) has one Hydrogen atoms, i.e. an isocyanate-reactive functional group.With less than 1000 index, exist than active hydrogen atom Group, such as isocyanate groups that OH groups are less.
Index is calculated by formula 1：
Wherein：
IN：Index
nISO：The total moles fraction of the molecule containing NCO, is represented with mole,
nOH：The total moles fraction of reactive hydrogen, particularly molecule containing OH (polyalcohol), is represented with mole,
fISO1：The degree of functionality of isocyanates 1,
nISO1：The molar fraction of isocyanates 1,
fP1：The degree of functionality of polyalcohol 1,
nP1：The molar fraction of polyalcohol 1.
Polyurethane Preparation Method is general knowledge.For example, polyurethane can pass through isocyanates and isocyanate-reactive compound React and prepare in the presence of catalyst and optional conven-tional adjuvants.
Starting ingredient and method for preparing preferred polyurethane is for example as described below.Citing describes generally to use below In the component for preparing polyurethane：Isocyanates A, isocyanate-reactive compound (B), and optional catalyst D and/or auxiliary Agent E, the catalyst D promotes diisocyanate A NCO group and synthesis component B, also referred to as anti-between the hydroxyl of polyalcohol Should.
Isocyanates A and isocyanate-reactive compound (polyalcohol) B also referred to as synthesizes component.
Component used according to the invention：
It is real using commonly known symmetrical aliphatic isocyanates, preferably diisocyanate as organic isocyanate (A) Example for three-, four-, five-, six-, seven-and/or eight methylene diisocyanates, 1,4- and/or double (the NCO first of 1,3- Base) hexamethylene (HXDI), 1,4- cyclohexane diisocyanates, 4,4 '-, 2,4 '-and 2,2 '-dicyclohexyl methyl hydride diisocyanate (H12MDI), preferably hexamethylene diisocyanate (HDI), 4,4 '-, 2,4 '-and 2,2 '-dicyclohexyl methyl hydride diisocyanate (H12MDI), more particularly hexamethylene diisocyanate.
We should be understood that symmetrical isocyanates is isocyanates, in the case of isomer mixture, main isomer For symmetrical molecule and with the isocyanate groups of two same reactions.
The inventive method uses isocyanates substantially.Substantially, TPU means in addition to main isocyanates, also to make here It is less than 5%, more preferably less than 3%, particularly preferably less than 1 weight % other isocyanates with based on isocyanates.Do not include wherein The oligomer as caused by isocyanates addition reaction；These products are included in basic isocyanates.
As isocyanate-reactive compound (B), can be used commonly known and different comprising preferred hydroxyl and/or amino Polyisocyanate reactant compound, compound B number-average molecular weight (Mn) is at least 2200g/mol, and condition is if compound B is Sebacate, then it is at least 950g/mol.It is preferred that polyesterols, Aethoxy Sklerol and/or PCDL, with generally going back collectivity Referred to as " polyalcohol ".Isocyanate-reactive compound, which has, is not more than 12000g/mol, preferably no greater than 6000g/mol, more Especially not greater than 4000g/mol number-average molecular weight (Mn), and preferably there is 1.8-2.3, preferably 1.9-2.2, more particularly 2 Degree of functionality.
All limiting values described in specification can be combined arbitrarily with all other limiting value, but in order to clear, not retouched Each is stated individually to combine.
Preferable isocyanate-reactive compound (B) is polyester-diol.
One further preferred embodiment is used in the polyester-diol with the mixture of PTMEG as isocyanic acid Ester reactive compounds (B), the polyester-diol are more particularly based on butanediol and adipic acid, with least 2200g/mol Number-average molecular weight (Mn).
PTMEG in the mixture, which has, is less than 2200g/mol and at least 500g/mol, at least more particularly 650g/ Mol number-average molecular weight (Mn).In an especially preferred embodiment, the PTMEG for mixing is polytetramethylene glycol. In an especially preferred embodiment, the mixture is used relative to the poly- of 1 weight of polyester glycol 0.05-1 parts by weight Ether glycol.
In another preferred embodiment of the present, the ester of decanedioic acid is used as isocyanate-reactive compound (B), the ester of decanedioic acid More preferably based on butanediol and with least 950g/mol number-average molecular weight (Mn).
Promote the suitable catalyst of the reaction between the NCO group of diisocyanate (A) and the hydroxyl of formation component (B) (D) it is by conventional tertiary amine known in the art, such as triethylamine, dimethyl cyclohexyl amine, N-methylmorpholine, N, N '-dimethyl Piperazine, 2- (dimethylamino ethoxy)-ethanol, diazabicyclo [2.2.2] octane etc., and particularly Organometallic compounds Thing such as titanate esters, iron compound, preferably ferric acetyl acetonade (III), tin compound, preferably oxalic acid tin, two tin octoates, two bays Sour tin, or the dialkyltin salts of aliphatic carboxylic acid, preferably tin compound.Catalyst is preferably with every 100 parts by weight of polyol (B) amount of 0.00001-0.1 parts by weight uses.
In addition to catalyst (D), conven-tional adjuvants (E) can also be added and be formed in component (A)-(B).Example includes surface-active Material, fire retardant, nucleator, oxidation stabilizers, lubricant and releasing agent, dyestuff and pigment, for example to resistant to hydrolysis, light, heat or The stabilizer of colour fading, inorganic and/or organic filler, reinforcing material and plasticizer.
As hydrolysis inhibitor, preferably using oligomeric and/or polymeric aliphatic or aromatics carbon imidodicarbonic diamide.For the stable present invention TPU is preferably added stabilizer in TPU with anti-aging.For the present invention, stabilizer is protection polymer or mixed with polymers The additive that thing influences to prevent disruptive environmental.Example is primary and secondary antioxidant, hindered amine as light stabilizer, UV absorb Agent, hydrolysis inhibitor, quencher and fire retardant.The example of commercial stabilizers is in Plastics Additive Handbook, and the 5th Version, H.Zweifel are edited, Hanser Publishers, Munich, 2001 ([1]), are provided in the 98-136 pages.If this hair Bright TPU under thermal oxide infringement, then can add antioxidant during use.It is preferred that use phenol antioxidant.Phenols The example of antioxidant is in Plastics Additive Handbook, and the 5th edition, H.Zweifel is edited, Hanser Publishers, Munich, 2001, provide in the 98-107 pages and the 116-121 pages.It is it is preferred that big using number-average molecular weight (Mn) In 700g/mol phenol antioxidant.It is preferred that the example of the phenol antioxidant used is that ((3,5- is double by 3- for pentaerythrite four (1,1- dimethyl ethyls) -4- hydroxy phenyls) propionic ester) (1010).Phenol antioxidant is typically with every kind of feelings The concentration of gross weight 0.1-5 weight %, more particularly preferably 0.1-2 weight %, 0.5-1.5 weight % based on TPU use under condition.
TPU is preferably stable by UV absorbents in addition.UV absorbents are absorption high energy UV light and the molecule for the energy that dissipates.Industry The middle customary UV absorber used for example belongs to such as the following group：Cinnamate, diphenyl cyanoacrylate, carbonamidine, benzal the third two Acid esters, diaryl butadiene, triazine and BTA.The example of business UV absorbents can be in Plastics Additive Handbook, the 5th edition, H.Zweifel is edited, Hanser Publishers, Munich, 2001, is found in the 116-122 pages. In preferred embodiments, UV absorbents, which have, is more than 300g/mol, particularly greater than 390g/mol number-average molecular weight (Mn). Furthermore it is preferred that the UV absorbents used, which should have, is not more than 5000g/mol, preferably no greater than 2000g/mol number-average molecular weight (Mn).BTA group is particularly useful as UV absorbents.The example of specially suitable BTA is213、328、571 Hes384 Hes82.UV absorbents preferably with based on TPU gross mass 0.01-5 weight %, more preferably 0.1-2.0 weight %, particularly 0.2-0.5 weight % amount is metered, every kind of In the case of the gross weight based on TPU.Stabilized and be generally still not enough to really based on the UV of antioxidant and UV absorbents as described above Break even good stabilities of the invention TPU to the damaging influence of UV ray.In such a situation it is preferred to except antioxidant and UV are inhaled Receive outside agent, hindered amine as light stabilizer (HALS) can be added in component (E) to obtain TPU of the present invention.HALS activity is based on it Formed intervene polymer oxidation mechanism nitroxyl radicals ability.HALS is the efficient UV stabilizations for most polymers Agent.HALS compounds are usually known and commercially available.The example of commercially available HALS stabilizers can be in Plastics Additive Handbook, the 5th edition, H.Zweifel, Hanser Publishers, Munich, 2001, find in the 123-136 pages.As Hindered amine as light stabilizer, preferably have greater than the hindered amine as light stabilizer of 500g/mol number-average molecular weight (Mn).Furthermore it is preferred that The number-average molecular weights (Mn) of HALS compounds 10000g/mol, especially preferably no more than 5000g/mol should be preferably no greater than.It is special Not preferable hindered amine as light stabilizer be double (1,2,2,6,6- pentamethvls base) sebacates (765, CibaAG) and 1- ethoxy -2,2,6,6- tetramethyl -4- hydroxy piperidines and butanedioic acid condensation production Thing (622).When the Ti content of product is<150ppm, preferably<50ppm, particularly<During 10ppm, very especially It is preferred that the condensation product of 1- ethoxy -2,2,6,6- tetramethyl -4- hydroxy piperidines and butanedioic acid (622)。HALS Compound is preferably used with 0.01-5 weight %, more preferably 0.1-1 weight %, particularly 0.15-0.3 weight % concentration, every kind of feelings Gross weight based on TPU under condition.Particularly preferred UV stabilize the phenol stabilizer comprising above-mentioned preferred amounts, BTA and The mixture of HALS compounds.
Can be in technical literature, such as Plastics Additive on other details of above-mentioned auxiliary agent and additive Handbook, the 5th edition, H.Zweifel is edited, and is found in Hanser Publishers, Munich, 2001.
TPU preparation can be by known method continuously, such as such as uses extruder, or belt method to pass through one way side Method or prepolymer process, or carried out in batches by known prepolymer process.In these methods, can by the component (A) of reaction, (B) sequentially or simultaneously react and be mutually mixed with optional (D) and/or (E), wherein reaction is immediately begun to., will in extruder method Component (A), (B), (D) and optional (E) are introduced into extruder individually or as mixture, and at 100-280 DEG C, preferably 140- Reacted at a temperature of 250 DEG C.Melt is pelletized and dried.
In an especially preferred embodiment, thermoplastic polyurethane be based on adipic acid or decanedioic acid and butanediol and Preferably as the HDI of polyisocyanates polyester.
Polyurethane of the present invention is used as hot-melt adhesive at elevated temperatures.It is preferred that by polyurethane at 50-160 DEG C, it is excellent 80-160 DEG C is selected, it is continuous at a temperature of 60-150 DEG C in another preferred embodiment of the present or melt in batches, and make the molten of them Body contacts with base material to be bonded.This application at least one surface to be bonded can be for example by roller, nozzle, with hot empty Air-flow carries out hot melt spin coating and hot-melt adhesive piece using hot press.In a preferred embodiment, hot melt is glued The application of mixture is bonded on base material to be bonded at once later.
Adhesive is particularly continuously applied, should after being applied on a surface to be bonded by hot-melt adhesive Surface with it is another optionally preheat merged with adhesive or surface without adhesive, and by the component preferably under stress simultaneously It is processed further with optional shaping.
Base material to be bonded is preferably fabric, metal, timber, woodwork, cork, ceramics, glass, including glass fibre, with And solid or foamed plastics such as ABS, PVC, polyolefin, polyurethane and neoprene, it is polychloroprene.TPU of the present invention is preferred For the purpose.Particularly preferred fabric, glass, polyurethane and polychloroprene.Herein, hot-melt adhesive of the present invention can use In very extensive application field.
In one embodiment, the present invention relates to comprising can be substantially by least one diisocyanate A and at least one The thermoplastic polyurethane that isocyanate-reactive compound B comprising hydroxyl and/or amino is obtained is as hot-melt adhesive Mechanograph, wherein：
- compound B number-average molecular weight (Mn) is at least 2200g/mol, condition be if compound B is sebacate, Then it is at least 950g/mol,
- diisocyanate A and isocyanate-reactive compound B react in the presence of the catalyst for sudden reaction,
- TPU does not include cahin extension agent,
- TPU has the index IN less than 1000.
Preferable mechanograph is roller, sole, the edging part of automobile, flexible pipe, coating, cable, section bar, laminated material, built Build the floor of thing and means of transport, plug connects, cable plug, mat, bellows, seat, foam, including by foaming in addition , hauling rope, solar cell module, windshield wiper blade, cable cover(ing), sealing, belt, non-woven fabrics, damping element, piece or fiber, It is preferably by being molded, rolling, powder sintered or extrusion.
The present invention further provides the mechanograph for including the bond vitrified agent using TPU used according to the invention.
Embodiment
Embodiment uses following components：
Table 1
Abbreviation Composition
ISO-1 4,4′-MDI
ISO-2 HDI
Polyalcohol 1 Number-average molecular weight (Mn) is 2500g/mol polyester-diol (butanediol-adipic acid)
Polyalcohol 2 Number-average molecular weight (Mn) is 1000g/mol polyester-diol (butanediol-decanedioic acid)
Polyalcohol 3 Number-average molecular weight (Mn) is 1000g/mol) polyester-diol (butanediol-adipic acid)
Polyalcohol 4 Number-average molecular weight (Mn) is 650g/mol (polytetramethylene glycol)
Using these components, compared as follows：
Embodiment 1 (compares)：
TPU is using two sad tin catalysts and from Werner and Pfleiderer, the Stuttgart spiral shell with 48D Bar cross-sectional length, the double screw extruders of ZSK 58 for being divided into 12 buckets are prepared by ISO-2 and polyalcohol 1 (OHN=46.0).TPU and Polyalcohol is proportionally used to obtain 970 index IN.Two tin octoates are with based on the use of gross mass 15ppm amount.To pelletize, Use the conventional wet comminutor from Gala (UWG).Material is then processed into injection-molded plaques (chip size：110×25×2). Test piece is heated 20 hours at 100 DEG C, and determines its mechanical performance.
Embodiment 2 (compares)：
TPU is using two sad tin catalysts and from Werner and Pfleiderer, the Stuttgart spiral shell with 48D Bar cross-sectional length, it is divided into the double screw extruders of ZSK 58 of 12 buckets by ISO-2 and polyalcohol 2 (OHN=112.6) preparation.TPU Proportionally used with polyalcohol to obtain 970 index IN.For granulation, it is granulated using the conventional wet from Gala (UWG) Machine.Material is then processed into injection-molded plaques (chip size：110×25×2).Test piece is heated 20 hours at 100 DEG C, and determined Its mechanical performance.
Embodiment 3 (present invention)：
TPU uses the screw sections length with 48D from Werner and Pfleiderer, Stuttgart, is divided into 12 The double screw extruders of ZSK 58 of individual bucket are prepared by ISO-2, polyalcohol 1 (OHN=46.0) and polyalcohol 4 (OHN=170.1).It is right In every weight polyol 1,0.57 weight polyol 4 is used.Polyol blends and isocyanates proportionally use with Obtain 970 index IN.Sudden reaction is carried out using two sad tin catalysts, wherein two tin octoates are with based on gross mass 40ppm Amount use.
It is determined that by the performance learned in table 2 below：
Table 2
By the embodiment of the present invention 3, it is clear that obtain the TPU with good mechanical properties.

Claims (19)

1. using by symmetrical aliphatic diisocyanate A and at least one isocyanate-reactive comprising hydroxyl and/or amino Melting adhered method of the thermoplastic polyurethane (TPU) that compound B is obtained as adhesive, wherein：
- diisocyanate A and at least one isocyanate-reactive compound B is anti-in the presence of the catalyst for sudden reaction Should,
- TPU does not include cahin extension agent,
- TPU has the index IN less than 1000,
- carried out in the absence of solvent at a temperature of 50-160 DEG C by the melting adhered of molten state TPU ,-using in gathering The polyester-diol of the mixture of ether glycol is based on butanediol and oneself as isocyanate-reactive compound B, the polyester-diol Diacid, has at least 2200g/mol number-average molecular weight (Mn), and there is the PTMEG number less than 2200g/mol to divide equally Son amount (Mn).
2. method according to claim 1, wherein TPU have the index IN less than 990.
3. method according to claim 1, wherein TPU have the index IN less than 980.
4. method according to claim 1, wherein isocyanate-reactive compound have terminal hydroxyl and/or amino.
5. method as claimed in one of claims 1-4, wherein index IN have 850-999 value.
6. method as claimed in one of claims 1-4, wherein index IN have 850-990 value.
7. method as claimed in one of claims 1-4, wherein index IN have 850-980 value.
8. method as claimed in one of claims 1-4, wherein diisocyanate are dicyclohexyl methyl hydride diisocyanate (H12MDI)。
9. method as claimed in one of claims 1-4, wherein diisocyanate are hexamethylene diisocyanate (HDI).
10. method as claimed in one of claims 1-4, wherein catalyst are tin compound.
11. method as claimed in one of claims 1-4, wherein polyester have the number-average molecular weight no more than 12000g/mol (Mn)。
12. method as claimed in one of claims 1-4, wherein polyester have the number-average molecular weight no more than 6000g/mol (Mn)。
13. method as claimed in one of claims 1-4, wherein polyester have the number-average molecular weight no more than 4000g/mol (Mn)。
14. method as claimed in one of claims 1-4, wherein compound B are the polyester based on butanediol and adipic acid.
15. method as claimed in one of claims 1-4, wherein compound B are the polyester based on butanediol and decanedioic acid.
16. method as claimed in one of claims 1-4, wherein TPU are used for bonding textiles, metal, timber, woodwork, pottery Porcelain, glass, and solid or foamed plastics.
17. method as claimed in one of claims 1-4, wherein TPU are used to be bonded cork.
18. method as claimed in one of claims 1-4, wherein TPU are used for adhering glass fiber.
19. include the bond vitrified agent using the thermoplastic polyurethane obtained according to the method for any one of preceding claims Film, injection or extruded product.
CN201180026152.3A 2010-03-29 2011-03-28 Use the hot melt adhesion of thermoplastic polyurethane Active CN102906146B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10158187 2010-03-29
EP10158187.4 2010-03-29
PCT/EP2011/054684 WO2011120895A1 (en) 2010-03-29 2011-03-28 Hotmelt adhesive bonding with thermoplastic polyurethane

Publications (2)

Publication Number Publication Date
CN102906146A CN102906146A (en) 2013-01-30
CN102906146B true CN102906146B (en) 2017-11-17

Family

ID=43836549

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201180026152.3A Active CN102906146B (en) 2010-03-29 2011-03-28 Use the hot melt adhesion of thermoplastic polyurethane

Country Status (6)

Country Link
EP (1) EP2552987B1 (en)
JP (1) JP2013527266A (en)
CN (1) CN102906146B (en)
BR (1) BR112012024535A2 (en)
ES (1) ES2459309T3 (en)
WO (1) WO2011120895A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012009055B4 (en) 2012-05-08 2015-06-03 Carl Freudenberg Kg Thermally fixable fabric, process for its preparation and its use as a lining material for fixing to an outer fabric
CN103865467B (en) * 2014-03-26 2018-04-10 广东裕田霸力科技股份有限公司 A kind of high-performance non yellowing type polyaspartic adhesive and preparation method thereof
DE102014211186A1 (en) * 2014-06-11 2015-12-17 Tesa Se Polyester polyurethane
DE102016007914A1 (en) 2016-06-30 2018-01-04 Lohmann Gmbh & Co. Kg Thermally activatable latently reactive adhesive film
CN106835711B (en) * 2017-03-06 2019-02-22 浙江华峰氨纶股份有限公司 A kind of preparation method of the polyurethane elastomeric fiber with Thermoadhesive energy
US20180361676A1 (en) * 2017-05-26 2018-12-20 Bemis Associates, Inc. Systems and methods for forming adhesive bonds
CN113861369A (en) * 2021-09-16 2021-12-31 山东一诺威聚氨酯股份有限公司 Low-melting-point high-viscosity high-strength thermoplastic polyurethane elastomer material and preparation method thereof
TWI800050B (en) * 2021-10-25 2023-04-21 南亞塑膠工業股份有限公司 Polyurethane hot melt adhesive
CN114479742B (en) * 2022-02-22 2023-10-20 河北邦泰氨纶科技有限公司 Bio-based high-crystallinity aqueous polyurethane adhesive for shoes and preparation process thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1639221A (en) * 2002-03-07 2005-07-13 旭硝子株式会社 Thermosetting polyurethane elastomer composition, polyurethane elastomer and process for production thereof

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1256822B (en) 1963-07-23 1967-12-21 Bayer Ag Bonding of plasticized plastics made of polyvinyl chloride or its copolymers
DE1930336C3 (en) 1969-06-14 1978-12-14 Bayer Ag, 5090 Leverkusen Use of polyurethanes for the production of adhesives with high green strength
DE3717070A1 (en) 1987-05-21 1988-12-08 Bayer Ag POLYESTER POLYURETHANES AND THEIR USE AS ADHESIVE
GB8728358D0 (en) * 1987-12-04 1988-01-13 Bostik Ltd Sheet materials
DE4035280A1 (en) 1990-11-07 1992-05-14 Bayer Ag MELT ADHESIVES
DE19519391A1 (en) 1995-05-26 1996-11-28 Henkel Kgaa Bonding process using partly crystalline solid adhesive tackified by friction which sets when left
DE19546657A1 (en) * 1995-12-14 1997-06-19 Giulini Chemie New hydrolysis-resistant aliphatic polyester amides, their production and use
DE69733255T2 (en) * 1996-07-08 2006-01-19 Vivoxid Oy BIODEGRADABLE MATERIAL WITH HIGH IMPACT STRENGTH
DE19700014A1 (en) 1997-01-02 1998-07-09 Henkel Kgaa Low-monomer PU prepolymer
DE10163857A1 (en) 2001-12-22 2003-07-10 Henkel Kgaa Reactive polyurethanes with a low content of monomeric diisocyanates
DE502004000020D1 (en) * 2003-07-10 2005-08-11 Wacker Chemie Gmbh Crosslinkable siloxane-urea copolymers
CN100523111C (en) * 2004-04-09 2009-08-05 大日本油墨化学工业株式会社 Moisture-curing type polyurethane hot-melt adhesive
US20050288476A1 (en) 2004-06-17 2005-12-29 Iskender Yilgor Thermoplastic copolymers through stoichiometric reactions between diisocyanates and oligomeric diols and diamines
JP2008069324A (en) * 2006-09-15 2008-03-27 Mitsui Chemicals Inc Water-disintegrating composition and water-disintegrating molded product containing water environment-responsive polymer having biodegradability

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1639221A (en) * 2002-03-07 2005-07-13 旭硝子株式会社 Thermosetting polyurethane elastomer composition, polyurethane elastomer and process for production thereof

Also Published As

Publication number Publication date
EP2552987B1 (en) 2014-03-19
ES2459309T3 (en) 2014-05-08
WO2011120895A1 (en) 2011-10-06
JP2013527266A (en) 2013-06-27
CN102906146A (en) 2013-01-30
BR112012024535A2 (en) 2020-07-28
EP2552987A1 (en) 2013-02-06

Similar Documents

Publication Publication Date Title
CN102906146B (en) Use the hot melt adhesion of thermoplastic polyurethane
EP2025730B1 (en) Moisture-curable polyurethane hot melt adhesive and multilayer sheet using the same
US10308754B2 (en) Composition
US8715799B2 (en) Thermoplastic polyurethane with antistatic properties
EP3022244B1 (en) Isocyanate prepolymer composition and crosslinked polyurethane prepared therefrom
CN102414236A (en) Soft thermoplastic polyurethane based on the ester of tricarboxylic acid
CN101054435B (en) Wet-type polyamine resin with hydrolyzation resistance and high peeling strength and preparing method thereof
KR101514107B1 (en) Urethane Prepolymer
CN1406258A (en) Polyurethane foams and method of manu facture thereof
US20110245449A1 (en) Melt adhesives containing thermoplastic polyurethanes
CN101400838A (en) Nonwoven based on thermoplastic polyurethane
JP2013532209A (en) Manufacturing process for blends of polylactide (PLA) and thermoplastic polyurethane (TPU)
KR101116291B1 (en) Method for manufacture high water permeable solvent free polyurethane adhesive
CA2746833A1 (en) Adhesion promoter for adhesive composites composed of plastic and of a polyisocyanate polyaddition product
JP2008138196A (en) Plastic composite material member and its manufacturing method
CN104379672A (en) Thermoplastic polyurethanes composition and preparation processes thereof
JP5615921B2 (en) Isocyanate group-containing prepolymer having good storage stability
KR101248479B1 (en) Hot melt type urethane adhesives resin composition
US9751279B2 (en) Composite elements composed from thermoplastic polymers and polyurethanes, and process for production thereof
CN101993520A (en) Isocyanate terminated prepolymer as well as preparation method and application thereof
JP4107032B2 (en) Solvent-free moisture-curable hot-melt urethane resin composition, foam, and sheet structure using the same
KR100581330B1 (en) Polyurethane porous structure of non-solvent type and method thereof using for artificial synthetic leather
KR101322761B1 (en) The manufacturing method of polyurethane coating resin composition
TW201114793A (en) Sprayable elastomeric polyurethane foam and process for its production
TWI794284B (en) Manufacturing method of synthetic leather

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant